3-chloro-1,2,4-thiadiazolyl-5 and 3-chloro-1,2,4-thiadiazolium-5 azo dyestuffs

ABSTRACT

A DYESTUFF OF THE FORMULA D-N=N-(B-N=N)(N-1)-A(-Z-A-N=N-D)(M-1) IN WHICH D ISQUATERNATED OR UNQUATERNATED 3-HALOGENO1,2,4-THIADIAZOLYL-5-, N IS 1 OR 2, M IS 1 OR 2, N AND M TOGETHER ARE 2 OR 3, Z IS A SINGLE BOND, AN OXYGEN OR SULFUR ATOM, AN IMIDO OR SULFONYL GROUP, OR A DIVALENT ORGANIC RESIDUE, B IS A 1,4-PHENYLENE RESIDUE THAT MAY BE SUBSTITUTED, AND A IS THE RESIDUE OF ACOUPLING COMPONENT, D, B,A ANDZ BEING FREE FROM SULFONIC ACID GROUPS.

UnitedStates Patent Office 3,732,201 Patented May 8, 1973 9 Int. Cl. C29b 29/10, 29/36, 29/38 US. Cl. 260-153 11 Claims ABSTRACT OF THE DISCLOSURE A dyestuff of the formula in which D is quaternated or unquaternated 3-halogenol,2,4-thiadiazolyl--, n is 1 or 2, m is l or 2, n and m together are 2 or 3, Z is a single bond, an oxygen or sulfur atom, an irnido or sulfonyl group, or a divalent organic residue, B is a 1,4-phenylene residue that may be substituted, and A is the residue of a coupling component, D, B, A and Z being free from sulfonic acid groups.

The present invention provides valuable azo dyestuffs that contain at least one quaternated or unquaternated 3-halogeno-1,2,4-thia-diazolyl-5-azo group.

The present invention also provides a process for preparing the above-mentioned dyestuffs, wherein a compound that contains at least one residue capable of acting as a coupling component is coupled with a diazotised 3- halogeno-1,2,4-thiadiazolyl-S-amine and then, if appropriate, quaternated. The coupling component may be a diazotisable compound, which may be diazotised and coupled with a further coupling component.

Preferred dyestuffs are those of the general formula especially those which are free from acid groups imparting solubility in water, in which D represents a 3-halogeno- 1,2,4-th-iadiazole or -thiazolium residue especially a 3- bromoor chloro-1,2,4-thiadiazole or -thiazolium residue and A represents the residue of a coupling component bound directly or through an azophenylene residue, A being especially a residue of a phenol, a naphthol, a pyrazolone, a pyridone, an aminopyrazole, an enolisable keto compound or an aniline, especially an alkylaniline.

The dyestuff may be further defined as an azo dyestuff of the formula wherein D is 3-chloro-1,2,4-thiadiazolyl-5 or 3-chloro-1,2, 4-thiadiazolium-5 and where A is the radical of a coupling component bound to the azo group via a carbon atom and selected from the group consisting of hydroxybenzene, hydroxybenzene substituted by lower alkyl-, lower alkoxy-, chloro-, lower alkylamino-, lower dia1ky1amino or alkanoylamino containing up to 8 carbon atoms, hydroxynaphthalene, indole or indole substituted by lower alkyl-, lower alkoxy-, chloro-, cyano-, nitroor phenyl-, S-hydroxypyrazolone, S-aminopyrazolone or said S-hydroxypyrazolone or S-aminopyrazolone substituted by lower alkyl, phenyl-, carboxy-, carbonamidoorcarbloweralkoxy-, 4-hydroXyquinoline-2, or 4-hydroXyquinoline-2 substituted by lower alkyl-, lower alkoxyor chloro-, tetrahydroquinoline or tetrahydroquinoline substituted by lower alkyl-, lower alkoxy-, lower cyanalkylor lower alkanoyloxy, malonic dinitrile, Z-hydroxy 4 methyl-5- cyano-G-pyridone, acetylacetone, dimedone, the term lower meaning that the radical contains at most 4 carbon atoms.

Further preferred dyestuffs are those of the general formula (DN=NA'-) Z in which D has the meaning defined above, A represents the residue of a doubly bound coupling component and Z represents a simple bond, an oxygen or a sulphur atom or an imido or sulphonyl group or a divalent organic residue containing no groups having dyestuff characteristics as well as the dyestuffs of the general formula in which D and A have the meanings defined above and A" represents an unsubstituted or substituted phenylene residue.

These compounds may be further defined as those of the formula where D is 3-chloro-1,2,4-thiadiazolyl-5 or 3-chloro-1,2,4- thiadiazoliurn-S e is H, CH OCH or Cl; is H or OOH A is hydroxybenzene, hydroXybenzene substituted by lower alkyl, lower alkoxy, chloro, lower alkylarnino, lower dialkylamino or C -alkanoylamino; S-hydroxypyrazole, S-aminopyrazole or said S-hydroxypyrazole and S-aminopyrazole substituted by lower alkyl, phenyl, carboxy, carbonamido or carbloweralkoxy or aminobenzene of the formula in which d is hydrogen, chlorine, bromine, lower alkyl, lower alkoxy, C C -alkylmercapto, phenyl, phenylmercapto, phenoxy, cyclohexyl or benzyl, c is hydrogen, chlorine, bromine, lower alkyl, lower alkoxy, C -C -alkylmercapto, phenyl, phenylmercapto, phenoxy, cyclohexyl, benzyl, trifluoromethyl, C -C -alkyl sulphonamido or C -alkanoylamino, C C -alkylsulphonic acid, p-toluene sulphonic acid, phenoxycarbonyl, C C -a1koXycarbonyl, ethoxycarbonylamino or aminocarbonyl; R and R each independently is hydrogen, lower alkyl, or lower alkyl substituted by benzyl, phenyl, chloro, cyano, (C -C alkoxy, glycidyl, hydroxy, nitro, carb(lower)alkoxy, formylamino, acetylamino, (lower)alkylcarbonyloxy, fiphenylsulphonyl, B-toluenesulphonyl, fi-p-chlorobenzenesulphonyl, B-methylcarbamyloxy, B-phenylcarbamyloxy, (lower)alkyloxycarbonyloxy, acetamidopropyl, nitrophenoxy, hydroxyphenoxy, (acetyl, cyano, hydroxy, methoxy or acetoxy)ethoxycarbonyl, cyanoethoxy, carboxy, acetyl, amino, diethylamino B-cyanoacetoxy, fi-benzoyl-fi-benzoyl- 8-hydroxy, benzoyloxy, 'phthaloylimido, Z-methyl-S-pyridyl, phenoxy, 4-methoxycarbonylbenzoyloxy, anisoyloxy, 2-chl0robenzoyloxy, phenylsulphonyloxy, phenoxyacetoxy, phenylthio, nicotinyloxy, 2-thiophenecarbonyl, methoxyacetoxy, phenylacetoxy or furoyloxy.

Specially preferred monoazo dyestuffs are those of the.

general formula in which d represents a hydrogen or halogen atom, a lower alkyl, alkoxy or mercapto group, an aryl, arylmercapto, or aryloxy group or a cycloalkyl, cycloalkylmethyl or benzyl residue, 0 has the same meaning as d or represents an acylamino group, and R and R each represents a hydrogen atom or a unsubstituted or substituted alkyl group, especially the monoazo dyestufis of the general formula in which hal' represents a bromine atom or preferably a chlorine atom and R R c and d have the meanings given above and more especially the dyestuffs of the general formula O! in which hal', R and R have the meanings defined above and c' and d each represents a hydrogen atom, methyl, ethyl, methoxy, ethoxy, phenylthio or phenoxy residue.

The groups may be further defined as follows: D is 3- chloro-1,2,4-thiadiazolylor 3 chloro-1,2,4-thiadiazolium-S; d is hydrogen, chlorine, bromine, lower alkyl, lower alkoxy, C C -alkylmercapto, phenyl phenylmercapto, phenoxy, cyclohexyl or benzyl; c is hydrogen, chlorine, bromine, lower alkyl, lower alkoxy, C -c -alkylmercapto, phenyl, phenylmercapto, phenoxy, cyclohexyl, benzyl, trifiuoromethyl, C -c -alkylsulphonamido or C -alkanoylamino, C1-C2'3lkYlS'lllPhOHiC acid, p-toluene sulphonic acid, phenoxycarbonyl, C C -alkoxycarbonyl, ethoxycarbonylamino or aminocarbonyl; R and R each independently is hydrogen, lower alkyl or lower alkyl substituted by benzyl, phenyl, chloro, cyano, (C C alkoxy, glycidyl, hydroxy, nitro, carb(lower)alkoxy, formylamino, acetylamino, (lower)alkylcarbonyloxy, 5- phenylsulphonyl, fl-toluenesulphonyl, 5-p-chlorobenzenesulphonyl, 5-methylcarbamyloxy, 5-phenylcarbamyloxy, (lower)alkyloxycarbonyloxy, acetamidopropyl, nitrophenoxy, hydroxyphenoxy, (acetyl, cyano, hydroxy, methoxy or acetoxy)ethoxycarbonyl, cyanoethoxy, carboxy, acetyl, amino, diethylamino, 5-cyanoacetoxy, 5-benzoyl-5-hydroxy, benzoyloxy, phthaloylimido, 2-rnethyl-5-pyridyl, phenoxy, 4-methoxycarbonylbenzoyloxy, anisoyloxy, 2- chlorobenzoyloxy, phenylsulphonyloxy, phenoxyacetoxy, phenythio, nicotinyloxy, 2-thiophenecarbonyl, methoxyacetoxy, phenylacetoxy or furolyoxy.

Apart from the groups mentioned above a may also represent a chlorine or bromine atom, a trifluoromethyl group or an acylamino group, which may be alkylated (preferably methylated) on the nitrogen atom, in which the acyl residue is the residue of an organic monocarboxylic acid, of an organic monosulphonic acid, for example, methanesulphonic, ethane-sulphonic or para-toluene monosulphonic acid, or the residue of a carbamic acid or of a carbonic acid monoester or monamide such as phenoxycarbonyl, methoxycarbonyl or aminocarbonyl.

The groups R, and R may each represent a hydrogen atom or a lower alkyl group (that is to say one which contains 1 to 4, preferably 2 to 4 carbon atoms), for example, a methyl, ethyl, n-propyl or n-butyl group, which may be substituted in the usual manner, for example benzyl, 5-phenethyl, halogenated alkyl groups, for example, 5 chlorethyl, 5,5,5 triiluorethyl, 5, dichloropropyl, 5-cyanoethyl, alkoxyalkyl, for example, 5-ethoxyethyl or fi-methoxybutyl, glycidyl, hydroxyalkyl, for example, 5-hydroxyethyl, 5,'y-dihydroxypropyl, nitroalkyl, for example, 5-nitroethyl, carbalkoxy, for example, 5- carbo (methoxy-, ethoxyor propoxy-)ethyl [in which the terminal alkyl group may contain cyano, carbalkoxy, acyloxy or amino groups in the w-position], 5- or 'y-carbo (methoxyor ethoxy)propyl, acylaminoalkyl such as 5- (acetylor formy1-) aminoethyl, acyloxyalkyl, for example, fi-acetyloxyethyl, 5, -diacetoxypropyl, 'y-butyryloxypropyl, 5-arylsulphonylalkyl, for example, 5-phenylsulphonylethyl, 5-toluenesulphonylethyl, fi-(p-chlorobenzenesulphonyl)-ethyl, alkylor arylcarbamyloxyalkyl, for example, fl-methylcarbamyloxyethyl and fi-phenylcarbamyloxyethyl, alkyloxycarbonyloxyalkyl, for example, 5-(methoxy-, ethoxyor isopropoxy-)carbonyloxyethyl, 'y-acetamidopropyl, 5 (p-nitrophenoxy)ethyl, 5 (p-hydroxyphenoxy) -ethyl, 5- (5'-acetyle,thoxycarb onyl) -ethyl, 5-[(5(-cyano-, hydroxy-, methoxyor acetoxy-)-ethoxycarbonyl1-ethyl, cyanoalkoxyalkyl, 5-carboxyethyl, 5-acetylethyl, 'y-aminopropyl, 5-diethylaminoethyl, 5-cyanoacetoxyethyl, 5-benzoyl-5- and (p-alkoxyor phenoxybenzoyl)-hydroxy-ethyl groups.

Preferably the groups R and R contain not more than 18 carbon atoms.

The azo dyestulfs may be prepared with the use of any desired coupling components, for example those of the benzene or naphthalene series or of the series of the heterocyclic coupling components. From among the coupling components of the benzene series there may be mentioned as well as the phenols, for example, mor p-cresol, resorcinol, 1-hydroxy-3-cyanomethylbenzene, especially the aminobenzenes, for example aniline, 3-methylaniline, 2- methoxy-S-methylaniline, 3-acetylamino-l-aminobenzene, N-methylaniline, N-5-hydroxyethylaniline, N-fi-methoxyethylaniline, N-5-cyanoethylaniline, N-5-chlorethylaniline, dimethylaniline, diethylaniline, N-methyl-N-(benzylor 5- phenylethyl)-aniline, N-n-butyl-N-5-chlorethylaniline, N- methyl-, ethyl, propyl, or butyl-)-N-5-cyanoethylaniline, N methyl-N-5-hydroxyethylaniline, N ethyl-N-5-chlorethylaniline, N-methyl-N-5-acetoxyethylaniline, N-ethyl- N-5-methoxyethylaniline, N-5-cyanoethyl-N-5-chlorethylaniline, N-cyanoethyl-N-(acetoxyor benzoyloxyethyl) aniline, N,N-di-u-hydroxyethylaniline, N,N-di-fl-acetoxyethylaniline, N ethyl-N,2-hydroxy-3-chloropropylaniline, N,N di 5 cyanoethylaniline, N,N-di-5-cyanoethyl-3- methylaniline, N 5 cyanoethyl-N-5"-hydroxyethyl-3- chloraniline, N,N-di-5-cyanoethyl-3-methoxyaniline, N,N- dimethyl-3-acetylaminoaniline, N-ethyl-N-5-cyanoethyl-3- acetylaminoaniline, N,N-di-5-cyanoethyl 2 methoxy-S- acetylaminoaniline, N-methyl N phenacylaniline, N-5- cyanoethyl-2-chloraniline, N,N-di-ethyl-3-trifluoromethylaniline, N ethyl N phenylaniline, diphenylamine, N- methyldiphenylamine, N methyl-4-ethoxydiphenylamine or N-phenylmorpholine; furthermore, for example, amines of the formula I CHzCHzOCHzCHzCN NHCOR';

in which R, and R,, have the meanings defined above.

Equally valuable results are obtained with a coupling component of the formula 1 I CHzCHzOClIzGHaCN CllzClIzOCO-Alkyl X2 NHCO CH! IllHCHO CHgCHzO CHnCHzCN N CH2CHzO COCH; NHCOGHa NHCH2CH2OCH2CH2ON,

NHGOCH;

OCH:

NHCHBOHzOCHROHiCN,

N HCOCH:

OC2H

NHCHzCHzOCHaOHrCN,

NHCOCH:

OCHa

NHCHZCHQOCOCHI,

NHCOCH:

NHCHzCHzOCHzCHzCN,

1 11100 OCzHI OCHa 1 11100 C H2 C H3 From the series of the coupling components of the naphthalene series there may be mentioned, apart from the naphthols, for example: 1- or Z-naphthylamine as well as 2-phenylaminonaphthalene, l-dimethylaminonaphthalene or 2-ethylaminonaphthalene. From the series of the heterocyclic coupling components there may be mentioned, for example, the indoles, for example, 2- methylindole, 2,5-dimethylindole, 2,4-dimethyl-7-methoxyindole, 2-phenylor Z-methyl-S-ethoxyindole, N48- cyanoethyl-2-methylindole, Z-methyl-S- or -6-chlorindole, 1,2-dimethylindole, l-methyl-Z-phenylindole, Z-methyl-S- n-itroindole, Z-methyl-S-cyanoindole, 2-methyl-7-chlorindole, Z-methyl-S-fiuor; or -5-bromindole, 2-methyl-5,7-dichlorindole or 2-phenylindole, 1-cyanoethy1-2,6-dimethylindole; pyridi'ncs such as 3-cyano-2,6-dihydroxy-4-methy1- pyridine; furthermore pyrazoles, for example l-phenyl-S- aminopyrazole or 3methylpyrazolone(5) or 1-phenyl-3- methylpyrazolone (5 1,3-dimethyl-pyrazolone (5 1- butyl-3-methylpyrazolone(5), 1 hydroxyethyl-3-methylpyrazolone (5 1-cyanoethyl-3-methyl-pyrazolone (5 1- (o-chloro-phenyl) S-methylpyrazolonefi), 3 carbomethoxy-pyrazolone(5); quinolines, for example, S-hydroxyquinoline, 1-methyl-4-hydroxyquinolone-(2), N-ethyl-3- 0xy-7-methylor N-fl-cyanoethyl-l,2,3,4-tetrahydroquinoline or pyrimidines, for example, barbituric acid, as well as 1,3-indandione, 1,8-naphthindandione, dimedone, acetoacetic acid anilide, m-hydroxy-N,N-diethylaniline, 3- hydroxy-4'-methyldiphenylamine, hydroquinone monomethyl ether, acetylacetone, S-hydroxybenzthiazole and 1,2-diphenyl-pyrazoline-3,S-dione.

Suitable fibre-reactive coupling components include, for example, 2,4-dichloro-6-['y(N-m-tolyl-N-ethylamino) propyl]-amino-1,3,5-triazine, N,N-di('y-chloro-fl-hydroxypropyl)-m-toluidine, 3-chloreacetylamino-N,N-dihydroxyethylaniline, 1 [3'-(5,1)-benzenesulphonyloxyetliylaminosulphonyl)phenyl]-3-methyl-5-pyrazolones and N,N-di (2,3-epoxypropylanilines). Further fibre-reactive coupling components have been mentioned in British patent specification No. 901,434, column 2, lines 66 to 125.

Further suitable coupling components include those which contain a quaternable or quaternated group, for example N-methyl-N,Z-dimethylaminoethylaniline, N,2- (N'-ethy1- N phenyl)-aminoethyl-pyridinium chloride; furthermore, for example, compounds of the formulae Further suitable coupling components are diazotisable amines, for example 1-amino-3-methylbenzene, l-amino- Z-methoxy-S-methylbenzene and l-aminonaphthalene, so that aminoazo dyestuffs are obtained which themselves can be diazotised and coupled with the above-mentioned coupling components to form disor polyazo dyestuffs.

Finally, there may also be used bifunctional coupling components, for example those of the formulae in which X, Y and Y each represents a hydrogen atom or a trifiuoromethyl, alkanesulphonyl, alkyl, alkoxy, aryloxy, arylthio or acylamino group or a halogen atom, R R and R each represents a hydrogen atom or an unsubstituted or substituted alkyl group, n=1, 2 or 3 and Z' represents a bridge member of the formula such coupling components, on both sides of which a 15 diazotised amine may be coupled, are:

CHzCHaCN NCCH2OH2 NCHzCHa-O C O-O-OHzC Hr-N- NC-CHzGHz-IYIH NHCHz CHzC N 3 U H3 C Hz):

0-CH: HaCO mores-O Orr-01m I ((5 IIsCa-N (Lo 00-0 o b mot-N0 Orv-02m l -CH3 I CHiCHz-O-C 0 CH3) Instead of a unitary diazo component there may be used a mixture of two or more of the diazo components according to this invention and instead of a unitary coupling component a mixture of two or more of the coupling components according to this invention.

The coupling components used in the present dyestuffs may also be divided into anilines, phenols, naphthols and compounds containing an active methylene group as defined, for example, in the textbook The Aromatic Diazo Compounds by K. H. Saunders, London, 1949, page 209.

The 3-halogeno-5-amino-l,2,4-thiadiazoles, especially the chloro derivative, have been described in Berichte, volume 93, page 2197 [1960].

The diazotisation of the afore-mentioned diazo components may be carried out, for example, with the aid of concentrated phosphoric acid and sodium nitrite or, for example, with a solution of nitrosylsulphuric acid in concentrated sulphuric acid.

The coupling may also be carried out by a method known per se, for example in a neutral to acid medium, if desired in the presence of sodium acetate or a similar buffer substance capable of influencing the coupling speed, or of a catalyst, for example dimethylformamide or pyridine or a pyridine salt.

However, rapid, possibly continuous mixing within a small space may be achieved, if desired, with other devices.

Owing to the nitrogen atom in the thiadiazole ring and also when the residue A contains a quaternable nitrogen atom, for example a pyridine group, the dyestuffs can be quaternated, and this is preferably done as the last process step.

The quaternization may be carried out by treatment with an ester of a strong mineral acid or organic sulphonic acid, for example with dimethyl sulphate, diethyl sulphate, an alkyl halide, for example, methyl-chloride, -bromide or-iodide, an aralkyl halide, for example, benzyl chloride, an ester of a lower alkanesulphonic acid, for example the methyl ester of methane-, ethaneor butanesulphonic acid or the alkyl esters of (4-methyl-, 4-chloroor 3- or 4-nitro)-benzenesulphonic acid that form as anions halogen, sulphuric acid semiesters, alkanesulphonic or benzenesulphonic acid anions, preferably at an elevated temperature in an inert organic solvent, for example in xylene, carbon tetrachloride, ortho-dichlorobenzene or nitrobenzene. Further suitable solvents include acetic anhydride, dimethylformamide, acetonitrile or dimethyl sulphoxide. The quaternated dyestuffs contain as anion Y- preferably the residue of a string acid, for example, sulphuric acid or its semiesters, or a halide ion, but they may also be used as double salts, for example with Zinc chloride, or in the form of free bases.

The new water-insoluble dyestufis, mixtures of these dyestuffs and mixtures thereof with other azo dyestuffs are very suitable for dyeing or printing leather, wool, silk and especially synthetic fibres, for example acrylic or acrylonitrile fibres, of polyacrylonitrile or copolymcrs of acrylonitrile with other vinyl compounds such as acrylic esters, acrylamides, vinylpyridine, vinylchloride or vinylidenechloride, or of copolymers of dicyanoethylene with vinyl acetate, or of acrylonitrile block polymers, fibres of polyurethanes, polypropylene fibres, especially polypropylene fibres modified with metals, especially with nickel, for example, cellulose triaoetate and ZVz-acetate and especially fibres of polyamides, for example, nylon-6, nylon-6,6 or nylon-l2 and of aromatic polyesters, for example of terephthalic acid and ethyleneglycol or 1,4- dimethylcyclohexane, and copolymers of terephthalic or isophthalic acid and ethyleneglycol.

Accordingly, the present invention includes also a process for dyeing or printing textile materials based on synthetic fibres, especially polyester fibres and polypropylene fibres modified with metal compounds or, when the dyestuffs are quaternated, on acrylic fibres, wherein a dyestuff of the formula which is free from acid groups imparting solubility in water is used, in which hal represents a halogen atom, preferably a chlorine atom, and B stands for the residue of a coupling component that is free from acid groups imparting solubility in water.

For dyeing in an aqueous dyebath the water-insoluble dyestuffs are advantageously used in a finely divided form, dyeing being carried out in the presence of a dispersant, for example, cellulose sulphite Waste liquor or of a synthetic detergent, or of a combination of different wetting and dispersing agents. As a rule it is advantageous to convert the dyestuffs prior to dyeing into a dyestuff preparation that contains a dispersant and the finely divided dyestulf in such a form that when the dyestufl" preparation is diluted with water a fine dispersion is obtained. Such dyestuif preparations can be manufactured by a method known per se for example by grinding the dyestuff of the dry or wet form with or without addition of a dispersant during the grinding operation.

When strong dyeings are to be produced on polyethylene terephthalate it is advantageous to add to the dyebath a swelling agent, or to carry out the dyeing process under superatmospheric pressure at a temperature above 100 C., for example at 120 C. Suitable swelling agents are aromatic carboxylic acids, for example salicyclic acid, phenols, for example, o-dichlorobenzene or diphenyl.

For thermosetting the dyestuff the padded polyester fabric is advantageously heated to a temperature above 100 C., for example a temperature ranging from 180 to 210 C., advantageously after first having been dried, for example in a current of warm air.

The dyeings obtained according to the present process may be subjected to an after-treatment, for example by heating with an aqueous solution of a nonionic detergent.

Besides impregnation methods, the dyestuffs indicated above may be applied according to the process of the invention by printing, using, for example a printing paste which contains apart from the auxiliaries conventionally used in the printshop such as wetting and thickening agents, the finely divided dyestuff.

By the process of the present invention strong dyeings and prints having good fastness properties are obtained.

The new water-insoluble dyestuffs may also be used for spin-dyeing polyamides, polyesters and polyolefins. The polymer to be dyed, advantageously in the form of powders, granules or chips, is mixed, as a spinning solution ready for use or in the form of a melt, with the dyestuff, which is introduced in the dry form of a dispersion or solution in a solvent, which may be a volatile one. After having homogeneously dispersed the dyestutf in the solution or melt of the polymer, the mixture is processed by a method known per se by casting, moulding or extrusion to furnish, for example, fibres, yarns, monofils and films.

The new dyestuffs are also specially suitable for dyeing metal-modified polyolefin fibres, especially nickel-modified polypropylene fibres, more especially when the coupling component contains a hydroxyl group in o-position to the azo group.

The quaternated dyestuffs obtained according to the present process contain as anion preferably the residue of a strong acid, for example of sulphuric acid, or of a semiester thereof, or of an arylsulphonic acid or a halogen ion. The anions introduced into the dyestuff molecule according to the process of this invention may, if desired, be replaced by anions of other inorganic acids, for example of phosphoric acid, sulphonic acid, or of organic acids, for example of formic, lactic or tartaric acid; in certain cases the free bases may be used instead. The dyestufi salts may also be in form of double salts, for example with halides of the elements of the second group of the Periodic Table, especially zinc chloride or cadmium chloride.

The quaternated dyestuffs and dyestuff salts obtained according to this invention may be used for dyeing or printing a wide variety of fully synthetic fibres, for example polyvinylchloride, fibres, polyamide fibres, polyurethane fibres, basically modified polypropylene fibres, basically modified polyester fibres and more especially polyacrylonitrile fibres.

The quaternated, water-soluble dyestuffs are in general only slightly electrolyte-sensitive and some of them are very readily soluble in water or in polar solvents. Dyeing with the quaternated, water-soluble dyestuffs is in general carried out in an aqueous neutral or acid bath, at the boil under atmospheric pressure, or at an elevated temperature under superatmospheric pressure. The commercial levelling agents may be used.

The invention is illustrated by the following examples. Unless otherwise indicated, parts and percentages in the following examples are by weight and temperatures are shown in degree Centigrade.

EXAMPLE 1 0.76 part of sodium nitrate is sprinkled at 0 to 10 C. into 9 parts of concentrated sulphuric acid. The mixture is heated at 65 C. until all has dissolved, then cooled to 0 C. and 10 parts by volume of a mixture of glacial acetic acid and propionic acid 4:1 are dropped in. A solution of 1.36 parts of 5-amino-3-chloro-1,2,4-thiadiazole in 15 parts by volume of 4: l-mixture of glacial acetic acid and propionic acid is added to the resulting solution and the whole is stirred for 3 hours at 0 to 5 C. 0.75 part of urea is added portionwise to this diazo solution. The resulting diazo solution is added at 0 to 5 C. to a solution of 2.43 parts of N-cyanoethyl-N-cyanoethoxyethylaniline in 30 parts of alcohol. The mixture is stirred for about 2 hours and then rendered neutral to Congo red with sodium acetate solution. On completion of the coupling the acetic and propionic acids are neutralised with sodium hydroxide solution. The precipitated dyestuff is filtered off and washed with water. It corresponds to the formula CzHrCN and dyes polyester fibres red shades having excellent fastness properties.

In an analogous manner dyestuffs are obtained when a diazonium compound of 3-chloro-S-aminothiadiazole is coupled with the coupling components listed in Column I of the following table. These dyestuffs dye polyester fibres the shades listed in Column II.

No. I

No. I II 6. N,N-di-B-acetoxyethyl3-acetamidoaniline Red-violet.

m-anisidine.

8. Diphenylamine Red.

9. N -B-eyanoethoxyethyl-2-methoxy-5-propiouyl- Violet.

amino-aniline.

10. 3-ctlianesulphonamidoaniline. Red.

N-benzyl-N-B-eyanoethylanilin Yellow-red. N-acetylmethyl-N-fi-phenoxyetli N-fl-cyanocthyl-N-fl-phcnylcarbonyle thyl Red.

toluldine. N-etl1yl-N-fl-phenoxycarbouylctliylaniline Red.

N-fi-cyanoethyl-N-fl-phenacetylaniline Red.

16. N fi-phenylaminocarbonylethyl-N -ethyl-rn- Blue-red.

toluidine.

cthyl-3-bron1aniline.

18. N-n-butyl-N-B-eyanoethyI-S-mcthansulphon- Violet.

amidoailine.

ethylaniline.

20. N-fi-hydroxyethyI-NB-cyanoethyl-3-pl1enoxy- Violetearbonyl-amino-aniline.

21 B-acetylaminodiphenylamine D0.

22. N-B-cyanocthyl-N-fi-n-butylaminocarbonyloxy- Red.

etliylaniline.

23. N-B-etlioxycarbonylethyl-N-flphenoxyearbonyl- Red.

oxy-ethylaniline.

24. N-fi-eyanethyl-N 13-methoxyethyl-3-benzoyl- Red-violet:

aminoaniline.

25. 1 -0 Oethyl-N-B-eyanoethyl-Sethylaniline Blue-r 26. N -fl-eyanoethyl-2-ehloraniline Yellow- 27 N -B-phenylsulphonylethyl-N -e thylaniline Blue-red- 28 N-fl-anis0yloxyethyl-N- -eyanoethyl-3- Do.

chloraniline. 29 N-B-(2-ehlorobenzoyl) oxyetllyl-N-cyano- Yellow-red.

methylaniline. 30 N-Baminocarbonyl-N-n-butyl-m-toluidine Ruby. 31- N -l -eyanocthyl-N-fl-phenylamino-earbonyl Red oxypropylaniline. 32 N-fi-gi henylsulphonylaminoethyl-N-propyl- Blue-red.

am me. 33 3-N-Bcyanoethylaminodiphenylether Yellow- 34- 3-N-B-eyanoethylaminodiphenylsulphide Red. 35 N fi-pl1enoxyacetoxyethyl-N-fl-eyanocthyl- Red.

am me. 36 N-B-Phenylthioethyl-N-B-ethoxycarbonyloxy- Blue-red.

etliyl3-ethylaniline. N 8-y-diliydroxypropyldiphenylaminc N-fl-phenyl-B-hydroxyethyl-N-cthylanilin N -B-propionyloxyethyl-N-B-cyanoethyl-2- Violet.

ethoxy-5-ethoxycarbonylaminoaniline. N-fl-aeetylaminoethyl-N-isopropylaniline Ruby- -v-mcotinyloxypropyl-N-fl-cyanoethyl-btrifluoro-methylaniline. 42. N-B-eyanoethyl-N-fi-(2-thiophencarbonyl)- oxyethylaniline. 43 N-B-e yanoethyl-N 8- (2'-cyanopro pionyl)- Red.

oxyethyl-B-bromaniline. 44 N-fi-eyanoethyl-N-B-methoxyaeetoxycthyl-3-(N Red-O methyl-N'-aeetyl)aminoaniline. 45 N-B-plienylaeetoxyethyl-N-fl-eyaiioctllylanilinm, Red.

46 N -B-2-f uroyloxyethyl-N-fl-methoxycarbonyl- Rubyethyl-3-ethoxyaniline. 47 3-N-B-cyanoethylaminodiphenyl Red.

48. 3-N-B-cyanoethylaminodiphenylmethane.

40 N -5-aeetoxyethyltetrahydroquinolino 50- N-B-hydroxyethyl-l-uaphthylaminc 51 2-naplat]iylaminefi-Sulphon-y-methoxypropylarm e.

53- l-phenyl-3-ethoxyearbonyl-fi-pyrazolone D0- 54- l-B-(B-mctl1oxycarbonyl)propionyloxycthyl- 3-mcthyl-5-pyrazolone. 55 1 3-11ydr0xyetliyl'3methyl-5-aminopyrazole Red-ycllo \v. 56 l-(4-1nethylphenyl)-3-mcthyl-Saminopyrazolc 57 1-plicnyl-3-1nethylaminopyrazole 0- 58 1-plienyl-3-n1ethoxy-5-an1inopyi Lolc. D 59 2-methylindole Orange- 00- 1.2-dimethylind0le. Do.

2,4-dimethylJ-methoxyindole 2-1nethyl-5-ehlorindole Z-phenylindolc 64 2-pl1enyl-5-niethoxyindole 0- 05- Carbonic acid-di-(B-N-;3-cyanoethyl-N- Red.

phenylainino)-ethylestcr. 0G- Adipic aoid-di-(fl-N- -cyanoethyl-N- Rod.

(phenylaminc)-ethylester. 07 Di-g-N-E-eyanoethyl-N -phenylaini no) ethyl- Red.

0 er. 6S. Hexamethylenediearbamie aeid-di-(B-N-fl- Red.

eyan0ethyl-N-m-toluylaminoethyl)ester. G9- 'Ihiophene-2,5-diearboxylic aeid-di(3-N. Red-violet.

N -bisaeetoxy-etl1ylamino) anilide.

Dyeing example 1 part of the dyestufi obtained above is ground in the wet state with 2 parts of an aqueous solution of 50% strength of the sodium salt of dinaphthylmethanedisulphonic acid.

This dyestuff preparation is stirred with 40 parts of an aqueous solution of 10% strength of the sodium salt of N-benzylt-heptadecyl-benzimidazoledisulphonic acid, and

12 then 4 parts of a solution of 40% strength of acetic acid are added. This mixture is diluted with water to obtain a dyebath of 4000 parts.

parts of a cleaned polyester fibre material are immersed in this bath at 50 C., the temperature is raised to l20l30 C. within half an hour and dyeing is performed for 1 hour under superatmospheric pressure at this temperature. The material is then thoroughly rinsed. A strong, pure red dyeing is obtained.

EXAMPLE 2 4.07 parts of 5-amino-3-chloro-1,2,4-thiadiazole are diazotised as described in Example 1. The diazo solution is run at 0 C. into a solution of 3.21 parts of m-toluidine in 50 parts by volume of methanol. The coupling mixture is rendered neutral to Congo red with sodium acetate solution. On completion of the coupling the acetic and propionic acids are neutralised with sodium hydroxide solution. The precipitated 3-methyl-4-(3-chloro-1,2,4-thiadiazole-5-azo) aniline is filtered otftf, washed with water and dried.

5.07 parts of the product obtained as described above are dissolved in 25 parts by volume of phosphoric acid, 1.5 parts of sodium nitrite are added at 0 C. and the whole is stirred for 2 hours at 0 C. Then 1.5 parts of urea are added and the batch is stirred for another 15 minutes. The resulting diazo solution is run at 0 C. into a solution of 1.9 parts of phenol in 10 parts of alcohol, and at the same time 15% sodium hydroxide solution is added so that the pH value of the coupling mixture remains between 7 and 8. The mixture is stirred for 4 hours at 0 C., then diluted with cold water, and the precipitated dyestutf is filtered off and washed free from salt. The resulting dyestuif of the formula No. I II III 1 3-anisidiuo Z-mcthylphcnol Brown-red. 2.- 3-eliloranilinc. 4-methylphenol o. 3.- 3-toluidine 3-methylpyrazolonc. Red. 4 2-n1ethoxy-5- 1-phenyl-3-inethyl Red.

methylaniline. pyrazolone. 5 3-toluidine N-ethyl-N-fl-cyanothyl- Blue-r011- aniline.

EXAMPLE 3 1.36 parts of 5-amino-3-chloro-1,2,4-thiadiazole are diazotised as described in Example 1. The diazo solution is added to a solution of 2.63 parts of 2'-(N-ethylanilino)- N-ethyl-pyridinium chloride in 50 parts of water at 0 to 5 C. The mixture is stirred for about 1 hour and rendered neutral to Congo red with sodium acetate solution. On completion of the coupling the reaction mixture is evaporated in a rotary evaporator. The residue is dissolved in water with heating and clarified by filtration. The filtrate is salted out. The precipitated dyestutf, is filtered ofi, washed with a sodium chloride solution of 10% strength and dried. The resulting dyestuif of the formula dyes polyacrylonitrile fibres red shades having excellent fastness properties.

In an analogous manner dyestuffs are obtained, which dye acrylic fibres the shades shown in column II of the following table, when diazotised B-chloro-S-amino-thiadiazole is coupled with the coupling components listed in column I.

NO. I II 1 ozHn Blue-red.

C21 1; Cl- CH:

2 CH3 Claret.

| /CHa Q caHaN 0711730 CH3 C2H4N NHC 0 CH3 4.- C2115 Blue-red.

N Br- Z 4N (C H3) 3 C1 5--.... /C2H4OCH3 Red.

N\ oHSooi- 6...... 02115 Blue-red.

V N\ Cl 7. Red.

/0 H2- ON\ 0113804 8 a 1 Red.

N CHgSOg C 21141? (CH3) 2 NH2 9. C Ha Red.

C -N 0113s 03- a B 2 a):

10...- C2H4CN Red.

-N cmsoio2H.- 1 I OH 11 /C2H4CN Red.

\ CH SO4 12...- /C2H4CN Red.

C2H-l0 C O CHzN (011 13.. Blue-red.

i C 2H4III a) 2 Dyeing example EXAMPLE 4 4.07 parts of 5-amino-3-chloro-1,2,4-thiadiazole are diazotised as described in Example 1. The diazo solution is added to a solution of 3.63 parts of N,N-dimethylaniline in parts by volume of methanol at 0 C. The coupling mixture is stirred for /2 hour and rendered neutral to Congo red with sodium acetate solution. On completion of the coupling the precipitated dyestuff is filtered off, washed free from salt and dried.

2.7 parts of the dyestufi obtained above are dissolved ture is diluted with water. The precipitated dyestutf is in 40 parts of warm chlorobenzeue. A solution of 1.5 filtered off, washed with water and dried. The dyestufi of parts of dimethylsulphate in parts of chlorobenzene is the formula dropped in and the mixture is stirred for 3 hours at 90 to 95 C. The reaction mixture is cooled and filtered. 5 fi f The filter cake is dissolved in hot water and clarified by N N filtration. The dyest-utf is precipitated with sodium chloride and zinc chloride. The precipitated dyestulf has the 5 I it formula g; Cl- ;-1 ICH; 01

N CN=N N CH Q a): after heat fixation or alkaline [fixation dyes polyamide S znche fibres red-violet shades having very good wet fastness properties.

In an analogous manner fibre-reactive dyestuffs are obtained when a diazonium compound of 3-chloro-5- amino-thiadiazole is coupled with the coupling components listed in column I of the following table. The dyestuffs dye nylon lfibres the shades shown in column II.

and is filtered off and dried. It dyes polyacrylouitrile fibres 1 violet shades having very good fastness properties.

In an analogous manner quaternated dyestuffs containing thiadiazoliniurn groups are obtained, which dye acrylic fibres the shades shown in column III of the following table, when diazotised 3 chloro 5 aminothiazole is coupled with the coupling components listed in column I and the dyestuif thus formed is then quaternated with the alkylating agent shown in column II.

Shade on synthetic No. 1 Ir III P 1 A u 0 n1 lul h 1 I H ni 'ne. irne ys ate B ue-red. 2.-." Z-methylanilin piToh r ei esulghonio acid Do. I II -e l yl-fig-cl loroaeezoxyethyli niling Redgiolet.

met y ester. -e y- -e oroace amino-moui ine o. 3 3-methyl-6-methoxy. p-Toliuenetslililphotnie D0. 3 3-0:,fi-fillbromopropionylamino-N,N-diacetoxyethyl- Violet.

aei me y es er. am no. 2... g-8g(1%tfiml0&1%infi i-. Dietiyl suphate V IDo. 4 2[N};rrit)a1th83g;iN-Nr;i-fithy-I-iph%nylamino- Red-violet.

.--.- -c 0r()- ie o i0 et. at y no -a no -c oro riazne.

aniline. y 5 2-[N-rnethyl-N-(fi-Nethyl-Nphenylamiuo- D0. 6..... N-methyl-N-hydroxydo Do. ethy1)]-an1ino-4-methoxy-6-ehlorotriazlne.

ethylanlline. 6 G-[N-methyl-N-(fl-N'-ethyl-N-phenylamino- Do. 7 N, N -dihydroxyethyl- Benzyl bromide Do. ethyl) amiuo-2,4-5-triehloropyrimidlne.

aniline. 7 2,3'diehloroquluoxaline-fi-carboxylic acid-[N-(fl- D0. N-phenylmorpholiue..-. Ethyl bromide Do. N-ethyl-N,m-toluy1aminoethyl)l-amide. 9 B-Br-N-methyl-N- Ethyl iodide D0. 8 z-[N-methyl-N-(B-N'-methyl-N-phenylamiuo- Do.

methoxyethylanlline. ethyl)]4,6-d1fiuorotrlal1ne. 10 N-etliyl-N-cyauethyl- .do Do.

aniline. 11.-.- N-butyl-N-chloro- Methyl iodide... D0.

ethylanillne. 12 Dlphenylnmine -.do Do. 13..-. Tetrahvdroquinoliue. p-Toluenesulphonie Do. Dyeing example 14 N N d th 1 I acd butyl ester. D

h fifi g fifi g 0 10 parts of a nylon-6,6 knitted fabric (Helanca) ar 2-naphtllylamine g fg f g g gfig f ned'bmwnimmersed at 30 C. in a dyebath which contains in 400 16 2-me thylindole Dimethylsulphate. Orange-red. Parts y volume of Water P of acetic acld of 80% g'mggg g ig "g3 ggstrength and 2 parts of a 5% aqueous dispersion of the methoxylndole, compound obtained as described in Example 5, and has iggggfijg ggwg g8 Y 3;; a pH value from 4 to 5. During 45 minutes the whole is amino-pyragole. brown. heated to the boil and dyeing is performed for 30 minggggggggggg Methyl Vwlet- 5O utes at the boil. By adding sodium carbonate the pH value amino-ethunoD-ester. is then adjusted to 12 and boiling is continued for 30 gfg i fffigg gg' minutes. The textile material is then thoroughly rinsed N,N-dlmethylnniline Diethyl sulphate Do; with water and dried. The resulting brilliant violet-red dyeing contains a considerable portion of dyestufi that In an analogous manner 3-methyl-4-(3-chloro-1',2,4'- cannot be extracted.

thiadiazole-5-azo)-aniline as diazo component and N,N- The dispersions mentioned above are obtained by dimethylaniline as coupling component, followed by grinding a mixture of 20 parts of dyestulf, 140 parts of methylation with dimethyl sulphate, furnishes the dyewater and 40 parts of sodium dinaphthylmethane-disul- 1.36 parts of 5-amino-3-chloro-l,2,4-thiadiazole are diazotised as described in Example 1. The diazo solution g ffi zi i fif 25 3 3 32' gf gfif gfizfi 15 run at 0 mm a lsolutlon of Parts in 50 parts by volume of alcohol, while at the same time I S 'P'N p Phenylammoethyl]'ammo'ia'6' adding sodium hydroxide solution of 15% strength at dlflhlofotflallne 1B 100 Parts of acetone- C0l1P 11I1g such a rate that the pH value of the coupling mixture mlxtllre 1S rfindefed neutral (0 Congo fed with Sodlum remains at from 7 to 8. The mixture is stirred for 4 hours acetate solution. On completion of the coupling the mixat 0 C., then diluted with cold water, and the precipi- 4.07 parts of 5-amino-3-chloro-1,2,4-thiadiazole are 1 7 tated dyestuff is filtered off and washed free from salt; it corresponds to the formula which dyes nickel-modified polypropylene materials redviolet shades having good fastness properties.

Dyestuffs that dye polypropylene the shades shown in column II of the following table are obtained in an analogous manner when a diazonium compound of 3- chloro-S-amino-thiadiazole is coupled with the coupling components shown in column I.

No. I II 1.. 4-methy1phenol Blue. 2 4-isopropylphenol Do. 3 4-cyclohexylphenol Do. 4- 4-eh1orophenol- Do. 4-methoxvphenol Do. 2, 4dimethylphenol Do.

Acetylacetone Yellow. 8 Dimedone Do. 9 1, 3-dimethylbarbitutic acid o. 10-.-. 3-dimethy1aminophenol Blue-red 11 3diethylaminophenoln. o.

2 3-ethylami nophenol. Red.

B-hydroxvdiphenylamin Violet.

3-hydroxy-4-methyldip en Do. 15 1-phenyl-3-methyl-5-pyrazo10ne Yellow-orange. 16 1-(4-chlorophenyl) -3-methyl-5-pyrazolone D0. 17 S-methylb-pyrazolone Do.

1 butyl-3-methyl-5-pyrazoloue. D0. 1-rnethy1-4rhydroxy-2 quinolone Yellow. 20 l-butyl-4hydroxy-2-quinolone Do. 21- 4-hydroxycumarine Do. 22-.-- 1, 2-diphenylpwazolidine-3, 5-dione D0. 23..-- 4, fidiphenylirnidazole Blue. 24-.-- 1,3-indandione Yellow. 25 Indoxyl Red-yellow Acetoacetic acid anilid 28.--. Malonie acid dinitrile 29 5, 6, 7, B-tetrahvdro-i-naphthol Violet.

30-... fi-chloro-lmaphth Do. 31 4-eth0xy-1-naphthol Do. 32 2-hydroxy-3-naphth0io acid but m1 Do. 33 B-hydroxyaeenaphthene Do. 34. Z-phenylaminonaphthalene Blue.

Printing example 1 part of the dyestutf of Example '6 together with 1 part of 1,1'-dinaphthylmethane2,2-disulphonic acid is ground in a ball mill to a fine aqueous paste containing 10% of dyestuff. Then, a mixture of 100 parts of this paste 310 parts of cold water parts of urea 500 parts of a 5% aqueous sodium alginate solution 40 parts of ammonium sulphate 1000 parts is prepared in a high-speed stirrer, and a nickel-containing polypropylene fabric is printed with the printing paste obtained in this manner. The printed fabric is dried, steamed for 30 minutes, rinsed in cold water, soaped for 20 minutes at C. with a solution containing per litre of water 1 to 2 g. of the condensation product of 9 mols of ethylene oxide with 1 mol of nonylphenol, and then rinsed in cold water. The red-violet print thus obtained has very good fastness properties.

I claim:

1. An azo dyestuif of the formula wherein D is 3-chloro-1,2,4-thiadiazolyl-5 or 3-ehloro-l,2, 4-thiadiazolium-5 and where A is the radical of a coupling component bound to the azo group via a carbon atom and selected from the group consisting of hydroxybenzene, hydroxybenzene substituted by lower alkyl-, lower alkoxy-, chloro-, lower alkylamino-, lower dialkylaminoor alkanoylamino containing up to 8 carbon atoms,

hydroxynaphthalene, aminonaphthalene, indole or indole substituted by lower alkyl-, lower a1koxy-, chloro-, cyano-, nitroor phenyl-, S-hydroxypyrazolone, S-aminopyrazolone or S-aminopyrazolone substituted by lower alkyl-, phenyl-, carboxy-, carbonamidoor carbloweralkoxy, 4- hydroxyquinoline-Z, or 4-hydroxyquinoline-2 substituted by lower alkyl-, lower alkoxyor chloro-, tetrahydroquinoline or tetrahydroquinoline substituted by lower alkyl-, lower alkoxy-, lower cyanalkylor lower alkanoyloxy, malonic dinitrile, 2-hydroxy-4-mcthyl-5-cyano-6-pyridone, acetyl-acetone, dimedone, the term lower meaning that the radical contains at most 4 carbon atoms.

2. dyestufI according to claim 1 in which A is a coupling component selected from cresol, resorcinol, l-hydroxy-3-cyanomethylbenzene, aminobenzene having the formula in which d is hydrogen, chlorine, bromine, lower alkyl, lower alkoxy, C C alkylmercapt0, phenyl, phenylmercapto, phenoxy, cyclohexyl or benzyl; c is hydrogen, chlorine, bromine, lower alkyl, lower alkoxy, C C -alky1- mercapto, phenyl, phenylmercapto, phenoxy, cyclohexyl, benzyl, trifluoromethyl, S C -alkyl sulphonamido or C -alkan0ylamino, C C -alkylsulphonic acid, p-toluene sulphonic acid, phenoxycarbonyl, C -C -alkoxycarbonyl, ethoxycarbonylamino or aminocarbonyl; R and R each independently is hydrogen, lower alkyl or lower alkyl substituted by benzyl, phenyl, chloro, cyano, (C C alkoxy, glycidyl, hydroxy, nitro, carb(lower)alkoxy, for'rnylamino, acetylamino, (lower)alkylcarbonyloxy, phenylsulphonyl, B-toluenesulphonyl, ,B-p-chlorobenzenesulphonyl, B-mcthylcarbamyloxy, ,B-phenylcarbamyloxy, (lower)alkyloxycarbonyloxy, acetamidopropyl, nitrophenoxy, hydroxyphenoxy, (acetyl, cyano, hydroxy, methoxy or acetoxy)ethoxycarbonyl, cyanoethoxy, carboxy, acetyl, amino, diethylamino, ,B-cyanoacetoxy, ,8- benzoyl-fl-hydroxy, benzoyloxy, phthaloylimido, Z-methyl 5 pyridyl, phenoxy, 4 methoxycarbonylbenzoyloxy, anisoyloxy, 2 chlorobenzoyloxy, phenylsulphonyloxy, phenoxyacetoxy, phenythio, nicotinyloxy, 2-thiophenecarbonyl, methoxyacetoxy, phenylacetoxy or furoyloxy; diphenylamine, N-phenylmorpholine, naphthol, l-naphthylamine Z-naphthylamine, Z-phenylaminonaphthaline, 1-dimethylaminonaphthalene, 2 ethylaminonaphthalene, indole, substituted by methyl, phenyl, cyano, cyanoethyl, methoxy, ethoxy, halogeno and nitro; l-phenyl-S-aminopyrazole, 3-methylpyrazolone(5) or 3-methylpyrazolone (S) substituted in the l-position by methyl, butyl, phenyl, chlorophenyl, hydroxyethyl or cyanoethyl; S-hydroxyquinoline, 1-methyl-4-hydroxyquinolone-(2), N-B-cyano ethyl-1,2,3,4-tetrahydroquinoline, barbituric acid, 1,3-indandione, 1,8-naphthindadione, dimedone, acetylacetone and S-hydroxybenzthiazole.

3. A dyestuff of the formula in which D is 3-ehloro-l,2,4-thiadiazolyl-5 or 3-chloro-l,2,4-thiadiazolium-S d is hydrogen, chlorine, bromine, lower alkyl, lower alkoxy, C -C alkylrnercapto, phenyl, phenylmercapto, phenoxy, cyclohexyl or benzyl c is hydrogen, chlorine, bromine, lower alkyl, lower alakoxy, C -C alkylmercapto, phenyl, phenylmercapto, phenoxy, cyclohexyl, benzyl, trifluoromethyl, C C alkyl sulphonamido or acyl C -alkanoylamino C -C alkyl sulphonic acid, p-toluene sulphonic acid, phenoxycarbonyl, C -C alkoxycarbonyl ethoxycarbonylamino or aminocarbonyl, R and R each independently is hydrogen, lower alkyl or lower alkyl substituted by benzyl, phenyl, chloro, cyano, (C -C )alkoxy, glycidyl, hydroxy, nitro,carb(lower)alkoxy, formylamino, acetylamino, (lower) alkylcarbonyloxy, phenylsulphonyl, fl-toluenesulphonyl, fl-p-chlorobenzenesulphonyl, fl methylcarbamyloxy, B- phenylcarbamyloxy, (lower)alkyloxycarbonyloxy, acetamidopropyl, nitrophenoxy, hydroxyphenoxy, (acetyl, cyano, hydroxy, methoxy or acetoxy) ethoxycarbonyl, cyanoethoxy, carboxy, acetyl, amino, diethylamino, fl-cyanoacetoxy, ,Bbenzoyl- B-hydroxy, benzoyloxy, phthaloylimido, 2-methyl- 5-pyridyl, phenoxy, 4-methoxycarbonylbenzoyloxy, anisoyloxy, Z-chlorobenzoyloxy, phenylsulphonyloxy, phenoxyacetoxy, phenythio, nicotinyloxy, 2-thiophenecarbonyl, methoxyacetoxy, phenylacetoxy or furoyloxy.

4. An azo dyestuff as claimed in claim 3, wherein either or d stands for acylamino the acyl of which is selected from chloroacetyl and a,B-dibromopropionyl or R contains a group of the formula C C alkylene-c', wherein c is chloroacetylamino, a,fl-dibromopropionylamino, chlorotriazinylamino or chloropyrimidinylamino.

5. A dyestuif of the formula where D is S-chloro-l,2,4-thiadiazolyl-5 or 3-chloro-1,2,4- thiadiazolium-S; e is H, CH OCH, or Cl; 1 is H or OCH A is hydroxybenzene, hydroxybenzene substituted by lower alkyl, lower alkoxy, chloro, lower alkylamino, lower dialkylamino or C -alkanoylamino; S-hydroxypyrazole S-aminopyrazole or said S-hydroxypyrazole and S-aminopyrazole substituted by lower alkyl, phenyl, carboxy, carbonamido or carbloweralkoxy; or aminobenzene of the formula in which d is hydrogen, chlorine, bromine, lower alkyl, lower alkoxy, c -c -alkylmercapto, phenyl, phenylmercapto, phenyl, phenylmercapto, phenoxy, cyclohexyl or benzyl; c is hydrogen, chlorine, bromine, lower alkyl, lower alkoxy, C C -alkylmercapto, phenyl, phenylmercapto, phenoxy, cyclohexyl, benzyl, trifluoromethyl, C C -alkyl sulphonamido or C -alkanoylamino, phenoxy carbonylamino, C -C -alkoxycarbonylamino or alkylamino carbonylamino; R and R each independently is hydrogen, lower alkyl or lower alkyl substituted by phenyl, chloro, cyano, (C -C )alkoxy, glycidyl, hydroxy, nitro, carb(lower)alkoxy, formylamino, acetylamino, (lower)alkylcarbonyloxy, fl-phenylsulphonyl, [El-toluenesulphonyl, p-p-chlorobenzenesulphonyl, fl-methylcarbamyloxy, (lower)alkyloxycarbonyloxy, acetamldopropyl, nitrophenoxy, hydroxyphenoxy, (acetyl, cyano, hydroxy, methoxy or acetoxy)ethoxycarbonyl, cyanoethoxy, carboxy, acetyl, amino, diethylamino, p-cyanoacetoxy, fl-ben zoyl-fl-hydroxy, benzoyloxy, phthaloylimido, Z-methyl-S- pyridyl, phenoxy, 4-methoxy-carbonylbenzoyloxy, anisoyloxy, 2-chlorobenzoyloxy, phenylsulphonyloxy, phenoxyacetoxy, phenylthio, nicotinyloxy, Z-thiophenecarbonyl, methoxyacetoxy, phenylacetoxy or furoyloxy.

6. A dyestuff according to claim 4 where A is an aminobenzene of the formula @NRIIM N O O 9. A dyestulf of the formula 10. A dyestuif of the formula 11. A dyestuff of the formula C1CN c H u g a N=N s o=Hl-1 I-o 0-01 References Cited UNITED STATES PATENTS 2,659,719 11/1953 Dickey et al 260 XR 2,891,942 6/1959 Merian 260157 XR 3,221,006 11/1965 Moore et a1. 260--158 3,321,266 5/1967 Wunderlich et al. 260158 XR 3,392,164 7/1968 wllndellich 260158 3,483,180 12/1969 Ramanathan 260158 3,534,016 10/1970 Lange 260-207 3,398,134 8/1968 Ball et al. 260157 3,415,809 12/1968 Fisher et al 260-158 3,428,621 2/1969 Wallace et al. 260--158 3,453,256 7/1969 Dale et al 260158 FLOYD DALE HIGEL, Primary Examiner US. Cl. X.R.

8-41 B, 41 D, 71; 260-146 R, 154, 155, 156, 157, 158, 332.2 C, 463, 465 D, 465 E, 472, 475 R, 482 B, 485 J, 570.5 R

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 37322O1 1 Dated May 973 Inventor) VISVINATHAN RAMANATHAN It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 18, :line- 26, delete "S1" and insert C -5 line 75, delete "acyl" Signed and sealed this 9th day of July 19%.

(SEAL)- Attest:

'McCOY M-.GIBSON,JR.' c. MARSHALL DANN Attesting Officer Commissioner of Patents 

